Mafic flows of the Middle to Upper Ordovician Dunn Point Formation of eastern Canada were deeply weathered under warm and relatively humid conditions before being buried by subsequent flows. In the absence of superior plants, and in the context of relatively low atmospheric carbon levels, the soils developed alkaline groundwater conditions through mineral–water interactions, which resulted in an enhanced mobility of Al relative to Si in most palaeosols of that formation. Although the vegetation cover was volumetrically insignificant compared with that of subsequent geological times, it was apparently producing very efficient chelates, which, for most palaeosols of the succession, generated a well-defined cheluviation pattern for not only Al and Fe, but also and mainly Ti, which is typically immobile in modern soils. The resulting soils developed an Al–Fe–Ti-depleted upper horizon that was enriched in Si, probably through periodic ground saturation. Long-term climatic variations related to orbital cycles are inferred to have accounted for a second type of soil in the succession, which contrasts with the former by showing a Si-depleted and less Al–Fe–Ti-depleted upper horizon. Some soil material was substantially reworked by surface runoff, but such occurrences can be easily differentiated from in situ soil material in terms of texture, structure and composition. A thick overlying rhyolite flow is thought to be responsible for providing abundant K in solution, which was incorporated in the underlying basalt palaeosols as exchangeable cations within a probably montmorillonitic clay precursor to the Fe–Mg-rich phengite that later developed during deep burial and orogenic compression.